Basic acylated cyclic diamine



, Patented Feb.- 20, 194sv Y BASIC ACYIIATED GYCLIC DIAMINE Melvin De Groote, University City, and Bernhard Keiser and Charles M. Blair, Jr., Webster Groves, Mo., assignors to Petrolite Corporation,

Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Original application June 27, 1940,

Divided and this application October 4, 1941, Serial No. 413,696

5Claims. (Cl. 260-4045) This application is a division of our-pending Serial No. 342,716.

application Serial No. 342,716, filed June 27, 1940, which matured as U. S. Patent No. 2,262,357, dated November 11, 1941.

The object of our invention is to provide a new material or composition of matter that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions, but which may be used for other purposes or have uses in other arts that we have not yet completely investigated. For instance, the said new material or composition of matter may be used as a break inducer in doctor treatment of the kind intended to sweeten gasoline. See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton. Certain of the compositions of matter herein described are of value as surface tension depressants in the acidization of calcareous oil-bearing strata by means of strong mineral acid, such as hydrochloric acid. similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein de-- scribed as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No.- 2,233,382, dated February 25, 1941, to Melvin De Groote and Bernhard Keiser. As to using compounds of the kind herein described as surface tension depressants or demulsifiers, in combination with mineral acid for acidization of oilbearing strata, reference is made to U. S. Patent and comparable acetic acid derivatives, are usually water-soluble. I

As has been stated, the compounds are characterized by having present at least one acyl radical derived from a high molecular weight carboxy acid. Insofar that one can form secondary amides, as well as primary amides (i. e., compounds where two acyl radicals are attached to the same amino nitrogen-atom), it becomes obvious that one can introduce more than one acyl radical into a cyclic diamine, and still have present a basic amino nitrogen atom of the kind previously described. In the event a polyamine,

having more than two amino nitrogen atoms, is employed, one can introduce at least two acyl radicals to form only primary amides. Furthermore, if the polyamine is hydroxylated, one can introduce two acyl radicals into a diamine (i. e., at the hydroxyl position as an ester form) and still leave the diamine basic.

The expression higher molecular weight car boxy acids is an expression frequently employed to refer to certain organic acids, particularly No. 2,233,383, dated February 25, 1941, to Melvin De Groote and Bernhard Keiser.

We have discovered that the basic acylated derivatives of certain cyclic polyamines, and more especially, certain diamines, are particularly ef-' fective' for the various purposes herein described,

and particularly as demulsifiers for oil field emul- 1 sions. These acylated cyclic .diamines are characterized by the presence-of atleast one basic amino. nitrogen atom, i. e., an amino nitrogen atom which is not directly linked to'an aryl radical, and which has, not been acylated by the introduction of an acyl radical converting the same to an amide. their basicity combine readily with acids, such as the high molecular organic acids subsequently described, or with low molecular'organic acids,v

such asacetic acid, butyric acid, and the like, or' withmineral acids, such as sulfuric acid, hydrochloricacld, or the like, toyform salts. The salts of the strongmineral acids or low molecular organic acids, for instance, the hydrochlorides,

Such compounds by virtue of monocarboxy acids, having more than six carbon atoms, and generally, less than 40 carbon atoms. The commonest examples include the detergentforming acids, 1. e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, natmrally-occurring petroleum acids; such as naphthenic acids, and carboxy acids produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat difierent sources, and are different in structure, but can be included in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids including cap'rylic acid, butyric acid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, erucic acid, saturated andunsaturated higher molecular weight aliphatic acids, such as the higher fatty acids containing at. least eight carbon atoms, and including, in addition to those mentioned, melissic acid, stearic acid, oleic acid, ricinoleic acid, diricinoleic acid, triricinoleic acid,

- and vegetable oils, such as these mentioned; hy-

droxy and alpha hydroxy higher carboxylic, aliphatic and fatty acids, such as hydroxy stearic acid, dihydroxy-palmitic acid, dihydroxystearic acid, dihydroxy-behenic acid, alpha-hydroxy cap- 'ric acid, alpha-hydroxy stearic acid, alpha-hydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid, alpha-hydroxy cocoanut oil mixed fatty acids, alpha-hydroxy margaric acid, alpha-hydroxy arachidic acid, and the like; fatty and similar acids derived from various waxes, such as beeswax, spermaceti, montan wax, Japan wax, coccerin, and camauba wax. Such acids include carnaubic'acid, cerotic acid, lac-, ceric acid, montanic acid, psyllastearic acid, etc. As suggested, one may also employ higher molecular weight carboxylic acids derived, by oxidation and other methods, from paraflln wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; aralkyl and aromatic acids, such as benzoic acid, Twitchell fatty acids, naphthoic acid, carboxydipheny], pyridine carboxylic acid, hydroxybenzoic acid, and the like.

Other suitable acids includephenylstearic acid, benzoylnonylic acid, campholic acid, fencholic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

In some instances, obviously certain derivatives of dibasicacids would in essence act as if they were simply monocarboxylated acids, for instance, various phthalamic acids derived from phthalic anhydride, and amines, such as aniline, cyclohexylamine, octylamine, etc. Other similar amido acids can be derived by means of other comparable anhydrides. One may also employ materials such as ethyl ricinoleate monophthalate, etc., and also various acids which are derived from chloracetyl rlcinoleic acid and its analogs, by replacing a chlorine atom with a suitable monovalent hydrocarbon or an oxy-hydrocarbon radical.

Another source of suitable acids are those commonly referred to as lac acids, such, for example, as the acids derived from shellac. Such acids include various polyhydrox'y acids, for example, aleuritic acid, shelloic acid, and kerrolic acid.

As is well known, one may use substituted acids in which some other non-functional constituent enters the structure of the fatty acid. Forinstance, one may use aryl-, hydroxy-, alkoxy-, ch1oro-:-, keto-, and amino-derivatives. Generally speaking, however, it is always preferable to use the unsubstituted acid, particularly free from substituent's' which contain either oxygen or nitrogen atoms; Generally speaking, the'introduction of hydrocarbon radicals. regardless of source,

has little effect, except in altering the hydrophile hydrophobe balance.

One may also employ the blown or oxidized acids, such as blown ricinoleic acid, blown oleic,

etc., or estolides derived from blown oils. such as blowncastor oil, blown soyabean oil, etc.

Needless to say. the acids themselves need not be employed; but one may readily employ any functional equivalent, such as the anhydride, the acyl chloride, or the like. In some instances, the esters, especially in presence of a trace or a significant amount of water, act as the acid itself, in that the acid is liberated. Unless specific reference is made to a particular isomer, one may employ any isomer or mixture of various isomers, if the acid or acids are so available.

Various well-known cyclic diamines will serve to produce compounds of the kind herein contemplated by acylation with a high molar carboxy acid of the kind described. As an example, one may employ omega-amino-N-ethylpiperidine of the formula:

CHPCH! CHz-CHQ fifi-dichlordiisopropyl ether (CIC3H7OC3H7C1); gamma gamma dichlorodipropyl ether (ClCaHvOCaHvCl) flp dichlorodiisobutyl ether (CIC4H9OC4H9C1); ethylene chloride; propylene chloride; butylene chloride; up glycerol dichlorhydrin; a-gammaglycerol dichlorhydrin; methyl glycerol dichlorhydrin; polyglyc'erol dichlorhydrins; dichloroacetone 0 (CICHs-JL-CHaCl) derived from acetone; dichlonnethyl propyl ketone 7 011,01 CIhGl (CHr-C o-cn etc. V

For additional examples, see U. 8. Patent No.

,, 2,126,620, dated August 9, 1938, to Clifford.

Another suitable compound in which the acyl radicals form part of the cycle, is exemplified by certain basic products derived from the amino ethers of high molar acids, particularly higher fatty acids. Reference is. made to U. 8. Patent No. 1,958,529, dated May 15, 1934,- to Bockmiihl and Knoll. Although said patent is concerned with derivatives of hish fatty acids, obviously one can substitute high molarcarboxy acids of the kind previously described. In brief, such compounds are obtained by causing a salt'of an imino ether of. a. higher fatty acid formula:

ORi

wherein R stands for an aliphatic hydrocarbon radical with at least 10 carbon atoms, and R1 of the general pound of the general formula:

stands for alkyl, to react upon a diamino comwherein X1 and X2 stand for'hydrogen or alkyl,

an amino hydrogen atom present,'they may be i'urther acylated, as a rule, without detracting from their 'basicity. However, even without further acylation, such compounds are entirely satisfactory and may be illustrated by the following formulas:

CnHuC l npmmcinoi N-cm I On uC \NH- H2 The manufacture of piperidine-produces tw'c by-products in substantially significant amounts, which may be suitably employed. One is the mav terial known as dipiperidyl, which has the following composition:

(Nuclear hydrogen I atom not indicated) The other is piperldyl pyridine:

on, on,

H II:

Another suitable class includes piperazine and piperazine homologes; i. e., materials derived by reacting alkylene dichlorides with ammonia.

. SeeU. 8. Patent No. 1,951,992, dated March 20, 1934, to Perkins. disclosed the following two compounds:

, v v 3 which, in the case of ethylene dichloride, may be illustrated as follows: 1 W

For instance, a somewhat similar compound, amyl chloramylamine, is described in U. S; Patent No. 2,014,077, dated September 10, 1935, to Wilson. Obviously, an amino alkyl chloride can react with a cyclic diamine, for instance, dicyclohexylamine or cyclohexylamylamine or the like, in the following manner:

- mula;

For. instance, there is there cyclohexylamine, and the like. Jean-produce polyamines containing more than H Ncinlicl 4- BEN z in which D represents a cyclic nucleus and D."

may b the same, or may be diiierent.

However, one is not limited to an amino alkyl chloride, because obviously compounds containing divalent linking radicals of the type, previously described may be. treated with ammonia so as to give an analog of the amino alkyl chloride, which may be indicated by the following for- F in which T represents the divalent linking radical previously described in connection with dichloro diethyl ether and various other kindred compounds, including glycerol dichlorhydrin. Such compound of the kind exemplified by can react with numerous secondary cyclic diamines and even primary diamines to produce suitable cyclic diamines, which maybe acylated to, produce compounds of the type herein contemplated. For instance, such compound may be reacted with benzylamine, cyclohexylamine, di-

Similarly, one

may involve an arylamine such as aniline. If a compound so obtained is acylated, then if the acylradical replaces an amino hydrogen atom attached to the NT'radical previously described,

one obtains an acylated diamine which is not basic, because neither the amino nitrogen atom nor the aryl nitrogen atom show basicity. If, however, acylation results in the replacement of an aryl amino nitrogen atom, then the resultant compound containing the radical:

NT- r H is basic in character and may be employed. Ac-

As to the general procedure employed, although not concerned particularly with cyclic amines Attention is also directed to the fact that two types or compounds described, to wit, cyclic amido ethers and cyclic amidines, do not have the acyl group present unless in the latter instance the and cyclic amidines, the grouping:

or the like, reference is made to U. S. Patent No.

2,046,720, dated July 7, 1936, to Bottoms.

In view of what has been said previously, it is unnecessary to indicate the method of producing the acylated compounds. Such compounds are obtained in the same manner that one obtains an acylated derivative of an ordinary non-cyclic polyamine. In other words, the high molecular weight carboxy acid or its equivalent, such as the anhydride or acyl chloride, is simply heated with the elimination of water or the equivalent compound, with the formation of an amide; or if the amine is hydroxylated and contains no amino hydrogen atom, then acylation is obtained by means of an esterification reaction, i. e., a reaction involving an alcoholiform hydroxyl, which, in turn, is attached to an amino nitrogen atom. Some compounds may contain both reactive amino hydrogen atoms and reactive hydroxyl radicals. In such instances one may produce a mixture of esters and amides.

Example 1 Dicyclohexyl ethylene diamine is acylated with:

ricinoleic acid by admixture in equal molecular proportions and heating at approximately 160- 180 C. until the salt first formed into the amide.

Example 2 One mole of cyclic triethylene triamine, previously described, is acylated with one mole of oleic acid employing the same procedure as in Example 1, preceding.

Example 3 Omega-amino-N-ethylpiperidine and purified naphthenic acids derivedfrom Gulf Coast crude oil are reacted in equal molar proportions at approximately 180-200 C. until an acylated derivative, is obtained.

Example 4 A material having the following composition:

which is bis(hydroxyethyl) piperazine, is esterifled with two moles of ricinoleic acid.

Example 5 One mole of dipiperidyl, previously described, is acylated with one mole of abietic acid.

In the formation of some of the above amine compounds, it is well known, of course, that the elimination of hydrochloric acid reacts with any amine present to form a hydrochloride and the hydrochloride so formed must be eliminated by means of caustic soda or the like to liberate the base or the amine. For the sake of brevity, this step has not been described in'detail; but wherever such procedure is required, it should be obvious to one skilled in the art. v

is converted is included within the broadened definition of acyl, so that it may be considered as an acyl radical; and this is also an instance where the "acyl radical contributes part of the cyclic structure. Reference to the examples will show that they are diamines, and otherwise are properly included.

It may be well to emphasize that all the polyamines employed must contain at least onebasic amino nitrogen atom, i. e., an amino nitrogen atom not directly linked to an aryl radical and not acylated. Such amino nitrogen atom may, however, be Joined to an acyl radical by an intervening carbon atom chain or the equivalent, 1. e., the acyl radical may be introduced in the form of an ester linkage without converting the amino nitrogen atom to a non-basic'form. Needless to say, the amines described may be used as is," or in the form of salts or in any other suitable form, such as the base form obtained by combination with water.

As has been previously stated, our preference is to use a detergent-forming acid, particularly a fatty acid, and more specifically, ricinoleic acid, or at least, a hydroxylated fatty acid, to furnish the acyl radical. More specifically, we prefer to use a diamine, rather than a polyamine having more than two amino nitrogen atoms; and more specifically, our preference is a piperazine type of material, such as those which have been previously described.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as oxide extract obtained in the refining of petroleum, etc., may be employed as luents. similarly, the material or materials herein described, when employed as a demulsifying agent for resolving petroleum emulsions of the water-in-oil type may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone, or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, orin a form exhibiting both oil and water solubility, Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or' 1 to upon its ability to treat certain emulsions more 4 advantageously and at a somewhat lower cost than is possible with other available demulsifiers,

or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as 'the'majority of .oil field emulsions are concerned; but we have found thatjsuch a demulsifying agent has commercial value, as it will economically break or resolve oilfield emulsions in a number ofcases which cannot be treated as easily or at so low acost with' the demulsifying agents heretofore available. 5

In using the above described demulsii'ying agent to break a petroleum emulsion, said demulsifying agent is brought into contact with or caused to act upon the emulsion, in any of the various ways,

- or by any of the various ap aratus now generally used to resolve'or break petroleum emulsions with .a chemical reagent, the above procedure bein usedeither alone, or in combination with Other demulsifying procedure, such as the electrical dehydration process. y

Said demulsifying agent may be employed in connection with what is commonly known as down-the-whole procedure, i. e., bringing the demulsifying agent'in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is. decidedly feasible when the demulsifying agent is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification. 1

It is to be noted that none of the compounds above described contain a quaternary ammonium radical; and compounds of the type herein contemplated are characterized by freedom from quaternary ammonium radicals.

Having thus described our invention, what we claim and desire to secure by Letters Patent is:

1. A basic acylated cyclic diamine of the formula:

in which R: is a member of the class consisting of hydrogen atoms, alkyl radicals, cyclohexyl radicals, benzyl radicals, and radicals of the formula R100 and R1C0.0R:, in which R100 is the acyl radical of a high molecular weight monocarboxy acid having at least 8 and less than'40 carbon atoms; OR: is a divalent alkylene oxide radical selected from th class consisting of ethylene oxide radicals, propylene oxide radicals, andglycidol radicals: and R4 is a divalent aliphatic radical selected from the class consisting of alkyl, oxyalkyl, and hydroxyalkyl; with the added proviso that: (a) there must be at least one occurv rence of the radical RICO; (b) there must be at least one occurrence of an amino nitrogen atom free from direct linkage to an R100 radical; and (c) at least one occurrence of R; which must be a benzyl radical.

2. A basic acylated cyclic diamine of the formula:

v Rt

in which R3 is a member. of the class consisting of hydrogen atoms, alkyl radicals, cyclohexyl radicals, benzyl radicals, and radicals of the formula R100 and R1CO.OR2, in which R100 is the acyl radical of a higher fatty acidhaving at least 8 and not more than carbon atoms; OR: is a divalent alkylene oxide radical selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, and glycidol radicals; and R4 is a divalent aliphatic radical selected from the class consisting of alkyl, oxyalkyl, and hydroxyalkyl; with the added proviso that: (a) there must be at least one occurrence of the radical R100; (b) there must be at least one occurrence of an amino nitrogen atom free from direct link e to an R100 radical; and (c) at least one occurrence of R: which must be a benzyl radical.

3. A basic acylatled cyclic diamine of the formula:

' I Ra Ra N-RiN Rs \R:

in which R: is a member of the class consisting of hydrogen atoms, alkyl radicals, cyclohexyl radicals, benzyl radicals, and radicals of the .formula R100 and R1CO.OR2, in which R100 is the'acyl radical of a higher fatty acid having 18 carbon atoms; OR: is a divalent alkylene oxide radical selected from the class consisting of ethyl-, ene oxide radicals, propylene oxide radicals, and glycidol radicals; and R4 is a divalent aliphatic radical selected from the class consisting of alkyl,

oxyalkyl, and hydroxyalkyl; with the added proviso that: (a) there must be at least one occurrence of the radical R; (b) there must be at leastone occurrence of an amino nitrogen atom free from direct linkage to an R100 radical; and

(c) at least one occurrence of R: which must be I a benzyl radical. I

4. A basic acylated cyclic diamine of. the formula:

in which Rais a member of the class consisting of hydrogen atoms, alkyl radicals, cyclohexyl rad- R100 and R1C0.OR=, in which R100 is the acyl radical of an unsaturated higher fatty acid having 18 carbon atoms; OR: is a divalent alkylene oxide radical selected from the class consisting of ethylene oxideradic'als, propylene oxide radicals, and glycidol radicals; and R4 is a divalent aliphatic radical selected from the class consisting of alkyl, oxyalkyl, and hydroxyalkyl; with the added proviso that: (a) there must be at least one occurrence of the radical R100; (17) there must be at least one occurrence of an amino nitrogen atom free from direct linkage to an RiCO radical; and (c) at least one occurrence of R: which must be a benzyl-radical. g

5. A basic acylated cyclic diamine of the formula:

oxyalkyl, and hydroxyalkyl; with the added pro- 10 visc that: (a) there must be at least one occurrence of the radical R100; (b) there must be at least one occurrence of an amino nitrogen atom free from direct linkage to an R1CO radical; and (c) at least one occurrence of R: which must be a benzyl radical.

MELVIN DE GROOTE. BERNHARD KEISER. CHARLES M. BLAIR, JR. 

